Process for preparing oxyalkylated derivatives



PROCESS FOR PREPG OXYALKYLATED DERIVATIVES Louis T. Morison, Puente, and Woodrow J. Dickson,

Monterey Park, Calif., assignors to Petrolite Corporation, Los Angeles, Calif., a corporation of Delaware No Drawing. Application June 4, 1953 Serial No. 359,664

8 Claims. (Ci. 260-2333) This invention relates to the preparation of substantially anhydrous and substantially undiluted oxyalkylated derivatives of a particular class of oxyalkylation-susceptible organic compound which, because of certain characteristics they possess, are not otherwise oxyalkylatable to produce such derivatives.

oxyalkylation-susceptible organic compounds are characterized by their possession of labile hydrogen atoms, i. e., hydrogen atoms attached to oxygen, nitrogen, or sulfur. Their oxyalkylation may proceed with greater or lesser readiness; but oxyalkylated derivatives can be prepared from them.

The oxyalkylating agents conventionally employed to produce oxyalkylated derivatives are the lower alkylene oxides, ethylene oxide, propylene oxide, butylene oxide, glycid, and methylglycid. These may be defined as alphabeta alkylene oxides containing four carbon atoms or less. They may be employed singly, in sequence, or in admixture.

. Unfortunately, there are some situations, like those with which this invention is concerned, in which the employment of such conventional oxyalkylating agents is not practicable. Some starting materials, although inherently oxyalkylation-susceptible, are solids which are substantially insoluble in any of the oxyalkylation-resistant solvents available for use in the preparation of oxyalkylated derivatives.

For example, many oxyalkylation-susceptible solids are insoluble in xylene, which is a frequently used solvent in oxyalkylation procedures. Xylene is oxyalkylation-resistant and is readily separable from the oxyalkylation mass by simple distillation' Furtheremore, even though such starting materials may be soluble in a few unusual oxyalkylation-resistant solvents, the latter are themselves comparatively nonvolatile. Various ethers might in some cases be considered suitable solvents for the oxyalkylation-susceptible solid starting material. Such ethers, like the diethers of the polyglycols, in addition to being expensive, are not susceptible to easy separation from the oxyalkylation mass by distillation. Hence, they are not readily recoverable from the oxyalkylation mass by distillation, to leave an undiluted oxyalkylated derivative.

Some solids which are oxyalkylation-susceptible are in fact most soluble in water; but water is not an acceptable solvent for use in oxyalkylation processes employing the conventionally used alkylene oxides because it reacts with such alkylene oxides to produce polyglycols, during oxyalkylation.

We are aware that it has been proposed in the past to conduct oxyalkylations using the conventional alkylene oxides in aqueous .solutions, presumably on the assumption that the oxide did not react with the water. However, it is now established that such reaction with the water occurs tosome extent. The oxyalkylated mass produced in such aqueous systems therefore contains varying proportions of alkylene glycols as contaminants r 2,854,449 Patented Sept. 30,. 1958 or adulterants. Our process avoids this difliculty because it is conducted under substantially anhydrous conditions in all cases. The starting solid material, the catalyst, and the alkylene carbonates employed by us are all used in substantially anhydrous form;

Furthermore, many oxyalkylation-susceptible solids cannot be used in undiluted form in an oxyalkylation process .using the alkylene oxides,-and simply liquefied by heating prior to introduction of the oxyalkylating agent, because they undergo partial decomposition as they melt. If maintained at the temperature at which fusion just begins to be apparent, for a time such as 15 minutes, they undergo at least partial decomposition. If they exhibit such behavior in the presence of an oxyalkylation catalyst, like the alkali carbonates, they come within our class of suitable starting materials for use in our present process.

The foregoing statement of difliculties is applicable to greater or lesser extent to a number of oxyalkylation-susceptible compounds, including those recited below. The alkylene oxides are not usable for their oxyalkylation for the above stated reasons.

Our present inventionovercomes such difficulties and permits oxyalkylation of such materials to be accomplished by simple and inexpensive means. Thus, we employ as primary oxyalkylating agents the carbonates which are the counterparts of the foregoing alkylene oxides, viz., ethylene carbonate, propylene carbonate, butylene carbonate, hydroxypropylene carbonate, and hydroxybutylene carbonate. Of these, only ethylene carbonate and propylene carbonate are currently in commercial production, although the others will doubtless achieve similar commercial status in time.

More specifically, our invention relates to a two-step process for preparing substantially anhydrous, substantially undiluted oxyalkylated derivatives from an anhydrous, solid, oxyalkylation-susceptible starch compound, which solid satisfies one of the following two con ditions: (a) it is infusible; (b) it suffers at least partial decomposition if maintained at its beginning-of-fusion temperature for a period of at least 15 minutes in the presence of an oxyalkylation catalyst, and which solid is insoluble in oxyalkylation-resistant, distillation-separable solvents; which process consists in: (A) first react-.

ing said solid with at least one alkylene carbonate selected from the class consisting of ethylene carbonate, propylene carbonate, butylene carbonate, hydroxypropylene carbonate, and hydroxybutylene carbonate, in presence of an oxyalkylation catalyst; the proportion of alkylene carbonate employed being sufiicient to yield a product WhlCh is at least liquefiable at the temperature required to efiect its subsequent oxyalkylation using at least one alkylene oxide selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycid, and methylglycid; and (B) subsequently reacting such partially oxyalkylated derivative with at least one member selected from the aforesaid class of alkylene oxides.

Briefly described, our process is practiced by introducmg 1nto a suitable processing vessel the solid, oxyalkylation-susce'ptible starting material, preferably in finely divided form; the desired or required proportion of alkylene carbonate; and a minor proportion of an alkaline catalyst such as an alkali carbonate. The mixture is warmed, preferably with stirring. As the temperature reaches a certain critical level, usually somewhat above C., there is a vigorous eifervescence in which carbon dioxide is liberated, and the oxyalkylated derivative is formed. In such instances where the starting material is acidic, it is used at least partially in the form of a salt, e. g., an alkali salt such as may be produced in situ by adding enough alkaline catalyst to leave a slight excess over what is required to leave the mixture slightly alkaline.

It-is sometimes-desirable"tomodify this general procedure in variousminor ways. For example, the alkylene carbonate is introduced into a vessel and warmed until liquid. The catalyst is added. The solid, oxyalkylationsusceptible material isthen slowly introduced in'finely divided form, with stirring, and the temperature is slowly raised to the reaction point.

starting material is not great and where use of the firstdescribed procedure'above would produce a solid mass in the vesselwhich could not be readily handled thereafter.

In'our process, we usually employ only enough alkylene carbonate in. the -first step to produce a liquid or readilyliquefiablederivative, which contains a relatively" small proportion of axyalkyleneradicals. We then continue oxyalkylation using theconventional alkylene. oxides. Stated-another-wayythis two-step processis employed to produce,= first, intermediates; then more highlyoxyalkylatedproducts -are' prepared 'in' the second step using the. more economical;conventional alkylene 'oxides In the appended claims, we have specified that the intermediate product-prepared in the firststep of-the twostepprocess sh'allbe a 'liquid'or at least liquefiable at the temperature 'requiredto-efiectthe' oxyalkylation by use of the. alkyleneoxides-in'-the-second'step of our process. Said second step is conducted at conventional" oxyalkylation temperatures, usually-between about 100 C. and 200. C.

One incidental advantage ofusing 'the alkyene carbonates-for oxyalkylation is that they are relatively inert materials ascompared-with the alkylene oxides. Their use .therefore entails smaller hazards. Oxyalkylations using them are conductedwithgreater safety than if the alkyleneioxides were employed: Processing vessels are usually not required to be pressure resistant when the alkylene carbonates are employed, whereas ethylene oxide and propylene oxide for example, are required to be em-v ployed in pressure vessels because of their physical properties..

All oxyalkylationsusceptible starch compounds usable as starting materials do not react with equal readiness withthe. alkylenecarbonates-in ourprocess; Where the starting material, although presumably oxyalkylationsusceptible :asijudged by its'structure', is of very high molecular .weight, or where steric or other obscure influences are adverse, oxyalkylation may proceed at extremely slow rates. Ho'wevenif the starting material is oxyalkylationsusceptible,:its.oxyalkylation maybe accomplished in due time, by meansl-of the alkylene'carbonates mentioned above 100 Cz. Thenmaxirnusn feasible-oxyalkylation' temperature is of, course the decomposition temperature 65 for the mixture of solid startingmaterial, catalyst, and

alkylene carbonate, and above which temperature pyroly-' sis of thestarting materiahpolymerization of-the alkylene carbonate,-,or -othcr. ;undesired reaction beginsto oecurz" The oxyalkylation.catalystsemployed by us are usually the alkali carbonates. rsuch. as-sodium=- or potassium carbonate,-. in substantially anhydrous -fo'rrn. Where the starting material is acidic, at least sufiicientalkali car bonateshould be added to neutralize such acidity. There:

afterranadditional amount-of alkali carbonate is usually desirably includedto accelerate the oxyalkylation process;

Such procedural variation. is useful where-theoxyalkylation susceptibility' of the 4 However, in some instances the alkali-neutralized starting material is suflicientlyalkaline to supply the desired cata-' lytic influence, without addition of further amounts of alkali carbonate.

The finished oxyalkylated product will of course contain such inorganic catalyst. The catalyst will usually separate readily from the oxyalkylated mass on standing, especially if slightly warm. Since the residual proportions of catalyst in the supernatant product are usually of very small magnitude after such settling, we consider they do.

not materially dilute or contaminate our finished products.

In some instances, solid, oxyalkylation-susceptible substances, which may have been stated in the literature to have definite melting points, are nevertheless susceptible to progressive decomposition if maintained at or about the temperature at which they begin to fuse, for any period of time. Some such substances similarly undergo progressive deterioration if subjected to such temperatures in the presence of an alkaline material, like an oxyalkylation catalyst, for any period of time. Such substances Which, although they may have recorded definite meltingpoints, are unstable under oxyalkylatingconditions as described, are included among our usable starting materials.

We have therefore limited our usable starting materials. to those which are either (1) infusible or which (2) suffer at least partial decomposition if maintained at their beginningof-fu'sion temperature for a period of at least 15"minutes in the presence of an oxyalkylation catalyst. Additionally, such solid starting material must be insoluble in roxyalkylation-resistant, distillation-separable solvents, as already stated.

As the molecular weight of the alkylene carbonate rises, its reactivity with the starch compound starting materials is reduced. Since, for example, ethylene carbonate is more reactive than propylene carbonate, and propylene carbonate ismore-reactive than butylene carbonate, there maybe marked difierences in the speed of oxyalkylation when different alkylene carbonates are used. In marginal cases, it will be understood,.a starch compound startingmaterial may be oxyalkylation-susceptible in the sense. that it isreadily reactive toward ethylene carbonate or propylene carbonate, but;it may be rather insensitive toward butylene carbonate.

Our process may be practiced using more than one alkylene carbonate, and .in. addition, more than one alkylene oxide, to producemixed oxyalkylated derivatives. Inflsuch cases, thealkylene carbonates may be employed'in sequence or they may be employed as a mixture, as desired. The same is true of the alkylene oxides employed in our two-step process, which may be used in sequence or as a mixture.

The oxyalkylation-susceptible starting materials embraced within our present class have been termed starch compounds in the foregoing paragraphs. Naturally, they include starch itself. Starches from different sources are known to=have-difierent molecular weights. Higher-molecular-weight starches, although structurally oxyalkylation-susceptible,react only slowly in the present process, it must be recognized. The amylose fraction, i. e., the lower-molecular-weight component, of starches is readily oxyalkylation-susceptible forthe presentpurpose. The amylopectin -or higher-moleeular-weight component is definitely less susceptible. These components are separable'bymeans of hot water, the amylose constituting the water-soluble matter. Amylose has a molecular weight range of about 10,00050,000, whereas amylopectins molecular weight ranges from about 50,000 to about 1,000, 000. Our process-is readily applicable to starch components'having-molecularweights up to about 100,000. Above this level, reaction with the present alkylene carbonates is progressively slower.

Inulin is another polysaccharide which we include among the starch compounds usable in our process. Glyfound in the literature, decomposition begins to take place at its beginning-of-fusion temperature if maintained for a short time, especially in the presence of an alkali carbonate.

When starches are partially hydrolyzed, the dextrins (starch gum) are formed. These are a series .of progressively less complex molecules, forming gummy amorphous masses, and are useful as adhesives. Among the dextrins whose properties have beenv rather well established are a-dextrin or a-tetramylose, b-hexamylose, and a-octamylose. All three have been crystallized. The familiar soluble starch, which is a depolymerization product derived from starch, is closely allied to its parent, although of indefinite composition.

All the foregoing we refer to as starch compounds and include among the useful starting materials for our present process.

As examples of our process, in which the foregoing starting materials are usable, the following are typical but not exclusive.

In all cases, the apparatus employed to produce the products in the laboratory was a conventional resin pot assembly, fitted with a stirrer. This is a glass apparatus comprising a lower bowl or vessel, and an upper cap section containing several outlets, for the stirrer shaft, a thermometer, and a reflux condenser, and a charge hole fitted with a stopper. The design is conventional and need not be described further. Heat is supplied by a glass-textile heating mantle which fits the lower portion of the assembly, and which is regulated by inclusion of a rheostat in the electrical circuit. Such devices are likewise wholly conventional, and require no description here. Motor-driven stirrers, of the kind here used, and having stainless-steel or glass shafts and paddles, are likewise conventional laboratory equipment.

Example 1 We have warmed a mixture of 264 grams of ethylene carbonate and 5 grams of powdered sodium carbonate in a conventional resin pot assembly to about 125 C., with stirring, until the alkylene carbonate was melted. We continued stirring and added in small increments a total of 40.5 grams of potato starch, at the same time gradually raising the temperature over a period of about 2.5 hours to about 175 C. Carbon dioxide began to evolve. The temperature was further advanced to about 195-205 C. and maintained for a period of 3.7 hours. The reaction mass was dark brown, and rather pasty. It represented a marginal example of our product.

Example 2 We warmed a mixture of 528 grams of ethylene carbonate and 5 grams of powdered sodium carbonate in a resin pot assembly to about 125 C., with stirring, until the alkylene carbonate was melted. We continued stirring and added in small increments a total of grams of commercial corn starch. We then raised the temperature to about 180 C. in minutes and maintained it at between 180 and 195 C. for 2 hours, by which time carbon dioxide began to evolve. We continued heating at that temperature range, with stirring, for 1.5 hours, when the mass showed signs of gelling. We then added an additional 264 grams of ethylene carbonate and continued heating, at the same temperature for 1.5 hours, carbon dioxide being evolved during this time. The mass was liquid when cold. Additional heating at the same temperature for a total time of 6 hours resulted in little more carbon dioxide evolution. The mass seemed to gel as temperature was increased. It darkened somewhat in this time, but was still liquid when cold.

Example 3 We warmed a mixture of 264 grams of ethylene carbonateandS grams of powdered sodium carbonate about 115. C., with stirring, until the alkylene carbonate was melted. We continued stirring and added in small increments a total of 20 grams of commercial soluble starch, at the same time gradually increasing the temperature to about 150 C., where the mass approached homogeneity. Temperature was increased, with stirring, to between 175" and 198 C., for a period of 2.5 hours. Gas was evolved during this time, and the mass became thicker. The product was a very dark, viscous liquid.

Example 4 We have repeated Example 3, using soluble starch, but substituting 3.06 grams of propylene carbonate for the ethylene carbonate there used, and continuing the reaction,

for a'period of about 4 hours.

The product was a very dark, viscous liquid.

"Example 5 We have repeated Example 3, using soluble starch, but

substituting for the ethylene carbonate there used a mixi ture of 132 grams of ethylene carbonate and 153 grams of propylene carbonate. The procedure was otherwise the same as in Example 3, except that the time of reaction was 4 hours. The product was a very dark, viscous liquid.

Example 6 We have repeated Example 3, using soluble starch, but substituting for the ethylene carbonate there used 348 grams of butylene carbonate, and continuing the reaction for a period 0% hours. The product was a very dark,

viscous liquid.

Example 7 We have repeated Example 3, using soluble starch, but substituting for the ethylene carbonate there used 354 grams of hydroxypropylene carbonate. The reaction time was 8 hours. Theproduct was a very dark, viscous liquid.

Example 8 We have repeated Example 3, using soluble starch, but substituting for the ethylene carbonate there used 396 grams of hydroxybutylene carbonate. The reaction time was 8 hours. The product was a very dark, viscous liquid.

Example 9 We have repeatedExample 3, using soluble starch. Then, after transferring the reaction mass to a conven-' of propylene oxide, and have maintained the temperature during the second oxyalkylating step at about C. Maximum pressure was about 30 p. s. i. The second step consumed about 5 hours. The product was a dark, viscous liquid.

Example 11 We have repeated Example 9, except that after introducing the 132 grams of ethylene oxide we have introduced 348 grams of propylene oxide, at about 125 C. The time required to introduce this propylene oxide was about 7 hours. Maximum pressure was about 30 p. s. i. The product was a dark, viscous liquid.

Example 12 We have repeated Example 5 above. Then, after transferring the reaction mass to a conventional oxyalkylating autoclave, adding 5 grams of sodium hydroxide, and heating to about C., we have introduced into the mass, with stirring, a mixture of 132 grams of ethylene oxide and 174 grams of-propyleneoxid'e. Theseeond-oxyalkyl ating step consumedabout-' 8 hours2 Maximum pressure was about 40 p.= ssi. Tli=produetwas a viscousydafle liquid Example 13;. a I

we have repeated. Example. 3; but substituting for the. solubles'tarch'20 grams of glycogen.. The procedure was. otherwise the same as in Examplej.

Example '14 We have repeated Example:=3,:but substituting for the soluble. starch 20. grams of: inulina- The. procedure was otherwise the .sameasin' rExample 3.I The product was. a. viscous, .darkliquida I I Ekamplel5 We have repeated Example 3, but substituting for the soluble starch 20 grams of 'a' commercial grade of dextrin. Theiprocedurelwas; :otherwise :the:sameaassin- Example :3. The :product-was aiviscouspdarkuliquid.

Exampleil 6 We -have repeated- Example :3, but: substituting; for ;the soluble: starch;20. grams :of a-tetramylose; 1. The procedure-s. was otherwise the same as in Example 3. The product was a viscous, dark liquid.

We-have repeated Examplei8, .but; substituting forrthet. soluble starch 20 grams-of .b-ihexamylo'ser;,.The:p1;ocedure was otherwise the same as in Example 3. Thegzproductv. was a viscous, dark liquid.

Example 1 8 8 ly cmdeoiL-andbil-field"waters: They-are useful inbiochemical and -biologieal work in 'some cases Weficlainlz l5 A two-step process ionpreparing substantially anhy drous, -'-substantially =undiluted* oxyalkylated derivatives from an anhydrous, solid, oxyalkylation-susceptible starch compoundfiwhich solid satisfies one; of the following two conditionsw-(a) itis 'infusible; (b) it: suffers .at least partialidecomposition if maintained atnits beginning-oi fusiongitemperature forsa periodof-at least 15 minutes in the-presence. of :an: 'oxyalk-ylation. catalyst, and which solid: is insoluble :in :oxyallcylation-resistant, hdistillatiom separable'lsol-ventspwhich process consists in: (A) first reactingxsaid solid with atfsleast onealkylenecarbonate.

selectedifromztherclass; consisting. of ethylene carbonate, propylene carbonate, butylene canbonate hydroxypropyls' ene. -vcarbonate, and ehydroxybutylene carbonate; in .the

presence :ofxancalkaline:oxyalkylation catalyst; the. ;pro-:

portion of alkylene carbonate employed being suflicient' to yield a productwhi'ehsis liquidat the-temperature required toteflect itssubsequent oxyalkylation using 'at leasLone.

alkylene oxide selected from the class consisting ofvethyln EIIQFOXldC, propylene :oxide, .butylene, oxide, glycid,,and methylglycid;.; and (B). .subsequently preaeting suclrnparri tiallygoxyalkylated: derivative with, at least .one, member i selected'from the aforesaid class of 'aIkYICIIC oxides; .1

2. Theprocess of claim ,Lwherein the oxyalkylatiom susceptible-starting materialtis a starch.

3. The. process. of .claim 1, wherein the oxyalkylatione; susceptible starting materialis .a soluble-starch.

4. The process of .claim 1,- wherein the oxyalkylatiom: susceptible starting material, is; glycogen.

5. The process'of claim 2, wherein the oxylalkylation-- susceptible starting-material is inulin.

6. vThe process ofzclaim '1, wherein the oxyalkylationsusceptible starting material is dextrin;

7. The process of claim.-l, .wherein the oxyalkylationsusceptible starting material is an amylose.

8. The process of claim "1, wherein the oxyalkylationsusceptible starting material is b-hexamylose.

References Cited inthe file of this patent UNITED STATES PATENTS 2,516,634 Kesler et al July 25, 1950 Carlson Sept. 7, 1948' 

1. A TWO-STEP PROCESS FOR PREPARING SUBSTANTIALLY ANHYDROUS, SUBSTANTIALLY UNDILUTED OXYALKYLATED DERIVATIVES FROM AN ANHYDROUS, SOLID, OXYALKYLATION-SUSCEPTIBLE STARCH COMPOUND, WHICH SOLID SATISFIES ONE OF THE FOLLOWING TWO CONDITIONS: (A) IT IS INFUSIBLE; (B) IT SUFFERS AT LEAST PARTIAL DECOMPOSITION IF MAINTAINED AT ITS BEGINNING-OFFUSION TEMPERATURE FOR A PERIOD OF AT LEAST 15 MINUTES IN THE PRESENCE OF AN OXYALKYLATION CATALYST, AND WHICH SOLID IS INSOLUBLE IN OXYALKYLATION-RESISTANT, DISTILLATIONSEPARABLE SOLVENTS; WHICH PROCESS CONSISTS IN: (A) FIRST REACTING SAID SOLID WITH AT LEAST ONE ALKYLENE CARBONATE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE CARBONATE, PROPYLENE CARBONATE, BUTYLENE CARBONATE, HYDROXYPROPYLENE CARBONATE, AND HYDROXYBUTYLENE CARBONATE, IN THE PRESENCE OF AN ALKALINE OXYALKYLATION CATALYST; THE PROPORTION OF ALKYLENE CARBONATE EMPLOYED BEING SUFFICIENT TO YIELD A PRODUCT WHICH IS LIQUID AT THE TEMPERATURE REQUIRED TO EFFECT ITS SUBSEQUENT OXYALKYLATION USING AT LEAST ONE ALKYLENE OXIDE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCID, AND METHYLGLYCID; AND (B) SUBSEQUENTLY REACTING SUCH PARTIALLY OXYALKYLATED DERIVATIVE WITH AT LEAST ONE MEMBER SELECTED FROM THE AFORESAID CLASS OF ALKYLENE OXIDES. 